Chem
·
2023
·
IF 23.5
Pei Li,Xinliang Li,Ying Guo,Ao Chen,Rong Zhang,Yue Hou,Qi Xiong,Yanbo Wang,Ze Chen,Jiaxiong Zhu,Minshen Zhu,Chunyi Zhi
Anionic redox reactions would achieve a higher capacity than typical transition-metal-oxide cathodes, offering low-cost chemistry for advanced lithium-ion batteries. Li-Cl 2 chemistry using anionic redox reactions of Cl 0/−1 shows superior operation voltage (∼3.8 V) and capacity (756 mAh g −1 ). However, a redox-active and reversible chlorine cathode has not been developed in organic electrolyte-based lithium-ion batteries. Chlorine ions bonded by ionic bonding hardly dissolve in organic electrolytes, imposing a thermodynamic barrier for redox reactions. Meanwhile, chlorine gas is easily formed during oxidation. Herein, we report an interhalogen compound, iodine trichloride (ICl 3 ), as the cathode to address these two issues. In situ and ex situ spectroscopy data and calculations reveal that reduced Cl − ions are partially dissolved in the electrolyte, and oxidized Cl 0 is anchored by forming interhalogen bonds. A reversible Li-Cl 2 delivers a specific capacity of 302 mAh g −1 at 425 mA g −1 and a 73.8% capacity retention at 1,250 mA g −1 .
研究领域:
材料科学
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电化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2023
·
IF 9.5
Huixian Xie,Liping Tan,Zhuo Yao,Jiaxiang Cui,Xiaokai Ding,Zuhao Zhang,Dong Luo,Zhan Lin
Li-rich Mn-based layered oxides are proposed to be candidates for high-energy Li-ion batteries. However, their large-scale production is still hampered by poor rate capability and severe voltage decay. It was mainly attributed to the irreversible oxygen loss, which induces transition metal ion migration, electrolyte consumption, and structural evolution. Herein, we propose an effective strategy of phosphorylation, in which the phosphate ion is induced to remove the surface labile oxygen. It urges the Li2MnO3 component to transform to the spinel-like structure and promotes the anionic redox process, thus facilitating lithium-ion diffusion and improving structural stability. As a result, the Li2MnO3 component is more prone to be activated, with the capacity increased by 18% in comparison with the pristine one. It also exhibits a superior capacity retention of 86.1% after 150 extended cycles and better rate performance delivering a capacity of 148.1 mA h g–1 even at 10 C. The effective phosphorylation opens a new way to tune anion redox chemistry and obtain structurally stable materials.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
PubMed
高影响因子
Carbon Energy
·
2024
·
IF 19.5
Wenfeng Wang,Lu Zhang,Zeang Duan,Ruyue Li,Jiajin Zhao,Longteng Tang,Yiming Sui,Yadi Qi,Shumin Han,Chong Fang,Desong Wang,Xiulei Ji
Rechargeable aqueous zinc batteries are promising for large-scale energy storage due to their low cost and high safety; however, their energy density has reached the ceiling based on conventional cathodes with a single cationic redox reaction mechanism. Herein, a highly reversible cathode of typical layered vanadium oxide is reported, which operates on both the cationic redox couple of V 5+ /V 3+ accompanied by the Zn 2+ storage and the anionic O – /O 2– redox couple by anion hosting in an aqueous deep eutectic solvent electrolyte. The reversible oxygen redox delivers an additional capacity of ∼100 mAh g –1 at an operating voltage of ∼1.80 V, which increases the energy density of the cathode by ∼36%, endowing the cathode system a record high energy density of ∼506 Wh kg –1 . The findings highlight new opportunities for the design of high-energy zinc batteries with both Zn 2+ and anions as charge carriers.
研究领域:
材料科学
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电化学
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能源存储
✓ 已验证
DOI
高影响因子
Energies
·
2023
·Vol. 16
·期 18
·6740
·
IF 3.2
Qi Liang,Peirong Li,Yue Zhao,Supeng Chen,Jixiang Yin,Yingchun Lyu,Qiang Li,Qinghao Li
Cation-disordered rock salt (DRX) cathodes exhibit high specific capacity due to the simultaneous use of anionic and cationic redox reactions. However, DRX systems face severe challenges that limit their practical applications; a most important challenge is their poor rate performance. In this work, the structure and morphology of Li1.17Ti0.58Ni0.25O2(LTNO) were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), etc. In combination with various electrochemical characterizations, we found that the sluggish kinetics of anionic redox within LTNO can be the key reason for the inferior rate performance. By sample relaxation at moderate temperature and X-ray absorption near edge structure (XANES), the ligand-to-metal charge transfer process is verified to occur between O and Ni and exhibits a prolonged characteristic time of 113.8 min. This time-consuming charge transfer process is verified to be the very fundamental origin of the slow kinetics of oxygen oxidation and reduction. This claim is further supported by the galvanostatic intermittent titration technique (GITT) at different temperatures. These findings provide essential guidance for understanding and further optimizing cathodes with anion redox reactions not only in the context of DRX cathodes but also conventional Li-rich cathodes.Keywords:lithium-ion batteries;cation-disordered cathode;anionic redox reaction;sluggish kinetics
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
Nature Communications
·
2025
·Vol. 16
·期 1
·1-12
·
IF 15.7
Cai Congcong,Li Xinyuan,Li Jiantao,Yu Ruohan,Hu Ping,Zhu Ting,Li Tianyi,Lee Sungsik,Xu Nuo,Fan Hao,Wu Jinsong,Zhou Liang,Mai Liqiang,Amine Khalil
Triggering the anionic redox reaction is an effective approach to boost the capacity of layered transition metal (TM) oxides. However, the irreversible oxygen release and structural deterioration at high voltage remain conundrums. Herein, a strategy for Mg ion and vacancy dual doping with partial TM ions pinned in the Na layers is developed to improve both the reversibility of anionic redox reaction and structural stability of layered oxides. Both the Mg ions and vacancies (□) are contained in the TM layers, while partial Mn ions (~1.1%) occupy the Na-sites. The introduced Mg ions combined with vacancies not only create abundant nonbonding O 2 p orbitals in favor of high oxygen redox capacity, but also suppress the voltage decay originated from Na–O–□ configuration. The Mn ions pinned in the Na layers act as “rivets” to restrain the slab gliding at extreme de-sodiated state and thereby inhibit the generation of cracks. The positive electrode, Na 0.67 Mn 0.011 [Mg 0.1 □ 0.07 Mn 0.83 ]O 2 , delivers an enhanced discharge capacity and decent cyclability. This study provides insights into the construction of stable layered oxide positive electrode with highly reversible anionic redox reaction for sodium storage.
研究领域:
材料科学
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电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Applied Materials & Interfaces
·
2023
·
IF 9.5
Weijian Tang,Guojun Zhou,Chengzhi Hu,Afei Li,Zhangxian Chen,Zeheng Yang,Jianhui Su,Weixin Zhang
Owing to the capacity boost from anion redox activities, cation-disordered rock-salt oxides are considered as potential candidates for the next-generation of high energy density Li-ion cathode materials. Unfortunately, the anion redox process that affords ultra-high specific capacity often triggers irreversible O2 release, which brings about structural degradation and rapid capacity decay. In this study, we present a partial chlorine (Cl) substitution strategy to synthesize a new cation-disordered rock-salt compound of Li1.225Ti0.45Mn0.325O1.9Cl0.1 and investigate the impact of Cl substitution on the oxygen redox process and the structural stability of cation-disordered rock-salt cathodes. We find that partial replacement of O2– by Cl– expands the cell volume and promotes anion redox reaction reversibility, thus increasing the Li+ ion diffusion rate and suppressing irreversible lattice oxygen loss. As a result, the Li1.225Ti0.45Mn0.325O1.9Cl0.1 cathode exhibits significantly improved cycling durability at high current densities, compared with the pristine Li1.225Ti0.45Mn0.325O2 cathode. This work demonstrates the promising feasibility of the Cl substitution process for advanced cation-disordered rock-salt cathode materials.
研究领域:
材料科学
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电化学
✓ 已验证
DOI
高影响因子
ChemistrySelect
·
2024
·Vol. 9
·期 40
·e202404259
·
IF 1.9
Jiangwei Tao,Yixiao Qiu,Guangsu Tan,Shaoyu Yang,Wenda Li,Weiwei Wang,Yuzhu Wang,Chao Xu
Graphical This work provides in-depth investigation into the electrochemical and structural properties of O3-Na[Li 1/3 Mn 2/3 ]O 2 , a promising high-capacity anionic redox cathode material for sodium-ion batteries. Our findings also indicate that enhanced cycling stability and suppressed impedance increases can be achieved through optimized upper and lower cutoff voltages. Activating anionic redox is an effective strategy for enhancing the capacity of cathode materials in both lithium-ion and sodium-ion batteries. However, the fundamental mechanisms of O3-type sodium anionic redox cathodes remain poorly understood due to the limited availability of such materials, despite their inherent advantages such as high initial sodium content and high reversible capacity. Herein, we employ multiple characterization methods to elucidate the structural and electrochemical properties of O3-Na[Li 1/3 Mn 2/3 ]O 2 , a promising sodium anionic redox cathode developed recently, with a particular focus on the effect of cutoff voltages during electrochemical aging. Our synchrotron powder X-ray diffraction results indicate that charging the material to voltages above 4.1 V induces substantial structural changes, which compromise the structural and electrochemical reversibility of the material. This is corroborated by more rapid capacity decay and increased impedance, attributed to severe degradation on both the surface and in the bulk, as evidenced by the formation of lower valence manganese compounds. Furthermore, increasing the lower cutoff voltage for the discharge process effectively suppresses surface degradation, thereby improving cycling stability. This work offers a comprehensive understanding of a pivotal sodium anionic redox cathode material, providing valuable insights that can drive the development of advanced materials for sodium-ion batteries.
研究领域:
材料科学
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电化学
✓ 已验证
DOI
高影响因子
Energy Storage Materials
·
2024
·
IF 18.9
Yuyu Deng,Ting Jin,Chao Li,Tao Zhang,Wujiu Zhang,Shengjie Cui,Chao Shen,Lifang Jiao,Haitao Huang,Keyu Xie
Triggering anionic redox reaction (ARR) in layered oxide cathodes has emerged as an effective approach to overcoming the energy density limitations of conventional sodium-ion batteries (SIBs) solely based on cationic redox. However, the local structural deterioration and lattice oxygen loss associated with ARR remain challenging and unsolved, resulting in severe capacity and voltage decay. To address these issues, we herein present a lattice-strengthened P2-Na 0.66 Ca 0.03 [Li 0.24 Mn 0.76 ]O 2 (NCLMO) cathode. The introduction of Ca into the Na layers enables the compressed TMO 2 slabs and reinforced TM–O bonds (TM = Li/Mn). Moreover, the incorporation of Ca into the Na layers effectively mitigates the out-of-plane migration of Li and impedes the in-plane migration of Mn during the anionic redox. The reduction of ion migration reduces the variation of the local environment surrounding O and hinders the formation of TM vacancy clusters, significantly mitigating the loss of lattice oxygen. Consequently, NCLMO delivers an impressive capacity retention of 76.04% at 1 C after 200 cycles. Our findings highlight the significance of maintaining local structural stability and offer novel insights towards achieving highly reversible ARR in layered oxide cathodes for high-energy SIBs.
研究领域:
材料科学
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电化学
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能源存储
✓ 已验证
DOI
高影响因子
Energy Storage Materials
·
2024
·
IF 18.9
Wenyu Yin,Zhixiong Huang,Tengfei Zhang,Tianqi Yang,Houpeng Ji,Yujia Zhou,Shaojun Shi,Yongqi Zhang
Sodium-ion batteries (SIBs) have been proved as one of the most alternative to Lithium-ion batteries (LIBs) by the virtue of the abundant resources of Na. Among the cathodes, layered oxides stand out owing to their high energy density . The Jahn–Teller distortion, structural phase transition and oxygen release are main drawbacks of Mn/Ni based layered oxides. Hence, Li-Ni-Cu co-substituted Na 0.67 Li 0.1 (Mn 0.7 Ni 0.2 Cu 0.1 ) 0.9 O 2 (NLMNC) sample was prepared. The NLMNC sample exhibits the honeycomb-ordered superstructure at about 22° which is ascribed to cation ordering. By virtue of the Li-Ni-Cu co-substitute, the Jahn–Teller distortion of Mn is suppressed. Attributed to Li + migrating from the metal oxide layer to the interlayer and the Li + can play the part of pillar in the interlayer, NLMNC cathode displays the capacity retention rate of 82.5 % at 200 mA g −1 after 100 cycles. The anionic redox reaction of NLMNC is related to the addition of Li ions and O 2p non-bonding which is different from the anionic redox reaction of electrons removing from O 2p in the e g * (Ni–O) states of Na 2/3 Ni 1/3 Mn 2/3 O 2 . During charge process, peroxo O − emerges with the oxidation of lattice oxygen. During discharge process, the intensity of peroxo O − gradually decreases. DFT calculations were also carried out to reveal the reaction mechanism of NLMNC. The DFT results showed that the anionic redox reaction occurs near Mn ions, while the Ni ions are stable which is corresponding with our results. It is proven that such Li-Ni-Cu co-substituted NLMNC presents a promising cathode material for SIBs.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
ELECTROCHIMICA ACTA
·
2022
·
IF 7.336
Bizhe Su,Hanqin Liang,Xiaohui Zhao,Tao Zhang,Yu Zhou,Denis Y.W. Yu
Two sodium-rich transition metal (TM) oxides with the same spinel structure, Na 2 MoO 4 and Na 2 WO 4 have been investigated as cathode materials for Na-ion batteries for the first time. Although the oxidation state of TMs in the compounds are already at its highest value of 6+, both of them can be activated by anionic redox reaction during initial charge, as revealed by X-ray photoelectron spectroscopy, to give considerable reversible capacity between 1.2 and 4.7 V. In addition, ex-situ X-ray diffractometry (XRD) shows that both cathode materials undergo insignificant structural evolution during Na extraction/insertion, suggesting that the Mo-O 4 and W-O 4 tetrahedral framework are stable even when more than 1 Na is removed from the materials. Overall, Na 2 WO 4 shows larger amount of Na extraction/insertion and better cycle stability than Na 2 MoO 4 . This is likely due to better structural integrity and better stability of Na 2 WO 4 against oxygen loss from ex-situ XRD and differential electrochemical mass spectrometry results.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
Advanced Energy Materials
·
2023
·Vol. 13
·期 27
·2300746
·
IF 27.8
Yaoshen Niu,Zilin Hu,Bo Zhang,Dongdong Xiao,Huican Mao,Lin Zhou,Feixiang Ding,Yuan Liu,Yang Yang,Juping Xu,Wen Yin,Nian Zhang,Zhiwei Li,Xiqian Yu,Hao Hu,Yaxiang Lu,Xiaohui Rong,Ju Li,Yong-Sheng Hu
Na-ion batteries (NIBs) are promising for grid-scale energy storage applications. However, the lack of Co, Ni-free cathode materials has made them less cost-effective. In this work, Mg 2+ is successfully utilized to activate the oxygen redox reaction in earth-abundant Fe/Mn-based layered cathodes to achieve reversible hybrid anionic and cationic redox capacities. A high first charge capacity of ≈210 mAh g −1 with balanced charge–discharge efficiency is achieved without O-loss, showing a promising energy cost of $2.02 kWh −1 . Full cell against hard carbon anode without pre-sodiation shows energy density exceeding ≈280 Wh kg −1 with a decent capacity retention of 85.6% after 100 cycles. A comprehensive analysis of the charge compensation mechanisms and structural evolution is conducted. Voltage and capacity loss resulting from partially reversible Fe 3+ migration to the Na layer is confirmed, shedding light on further improvements for low-cost NIB cathodes in application scenarios.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2021
·
IF 8.128
Yueyue He,Shuo Wang,Haiyan Zhang,Xin Chen,Jin Li,Huiyuan Xu,Yanhui Zhang,KangHui Hu,Genpin Lv,Yan Meng,Wei Xiang
Li-rich disordered rock-salt cathode (DRX) materials with advantage of low cost, long cycle life, nature abundant resource and high power and energy density attracted a great deal of scholarly attention. However, the poor cycle stability and the unclear realization of cation and anion redox activity in low-cost element system have severely hindered the construction of high-performance DRX. Herein, a promising class of Ti-Mn based cathode materials Li 1.25 Mn 0.25 Nb 0.25 Ti 0.25 O 2 and Li 1.25 Mn 0.25 Ti 0.5 O 1.75 F 0.25 were designed and successfully synthesized to construct high energy density DRX and investigate the effect of fluorination on cation and anion redox activity. The results show that both fluoridized and unfluoridized DRX possess a similar structure ( Fm -3 m), but distinctly different charge/discharge profiles. The fluoridized cathode shows high initial charge/discharge capacity of 317.3/283.9 mAh g −1 , specific energy density of 1370.4/735.5 Wh kg −1 and stable capacity retention with a discharge capacity of 202.6 mAh g −1 after 20 cycles at 20 mA g −1 . Combining relevant spectroscopic results and HRTEM images, we revealed that the excellent cyclability of Li 1.25 Mn 0.25 Ti 0.5 O 1.75 F 0.25 is rooted in the weakened adverse effects of moderated oxygen redox and the reduced Jahn–Teller distortion effect resulting from Mn 3+ , endowing the fluoridized DRX with better structural stability and larger Mn 2+ /Mn 4+ reservoir. The strategy of constructing low cost oxyfluoride and the understanding of the mechanism of fluorination induced cation and anion redox activity would provide reference for the development of high-performance DRX materials.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）